Modification of fatty oils



from my copending' closed not only cations, including ,different methods are are also disclosed variations some for other p memo Oct- 1 1942' UNITED STATE,

MODIFICATION or rii'r'rr oms Lass-i6 Aooanoot Orange, N. I.

No Drawing.

Application February 5, Serial No. 129,662

Claims. (01. 260-401) GENERAL-mam or mos This invention relates to the modification or vention isconcerned with the bodying of fatty claimed'hereinis divided application Serial No. 318,650 of'which the present application is 9. continue;- tion-in-part, and said subject matter is disin said application 318,650 but also at least in part in certain other prior applications,'especiaily Serial No. No. 2,213,944), and Serial No. 143,786 (now Patent 2,189,772). t

Organic ,isocol oids are colloidal substances in which the dispersed phase and the dispersion.

The subject matter medium are both of the same chemical composition, although present state. In the bodying' organic isocolloids) the relation between the dispersed phase and the dispersion medium is altered, the dispersed phase being increased and the dispersion medium correspondingly decreased.

In accordance with various of my prior applithose mentioned above, various disclosed for modifying organic isocolloids, and especially for bodyin in a different physical ,iatty oils. 1 In general, the modification is brought about by heatingthe isocolloid inthe presence of a modifying agent. a a In the prior applications. various. different generic and sub-generic. classes and specific modifying agents are disclosed; and, in addition, there in process. ent modifying agents or groups thereof, and also variations in process, eifect different results,- some being of importance for certain purposes and Diiferthe in:

359,425 (now Patent of fatty oils' (which are I having good body and drying molecule an acidic inorganic residue and an organic residue. By an acidic inorganic residue I mean a residue capable of yielding an inorganic acid upon the addition of one or more hydrogen atoms or OH groups.' A

The subject matter ciaimed' herein relatesto the use of 2-radica1 type modifying agents in which the acidic inorganic residue is a nitrogenous residue. and is capable of yielding an inorganic nitrogen-containing acid upon the addition of hydrogen or a water -molecule, b -group'of agents having certain distinctive characteristics distinguishing it from other modifying agents in the general class, in which the inorganic radical does not contain nitrogen. The distinctive characteristics will be no ted out more fully hereinafter.

this Particular su Tun STABTING'MATEBIAL The fatty oils and similar materials withwhich the present application is especially concerned find one of their most important uses in the coating materials and plastics industries, especially the paint and varnish industry, 'where oils power are very important. Theimproved products produced in accordance with this invention also have many Gth'er' uses. a

A list of .typical oils which'may be" advan tageously modified by my vention is asqiollowsz Tung'oil Rapeseed oil Castor oil Walnut oil Linseed oil Pine seed oil Fish oil (train oils) Corn 011 ,Poppyseed oil Olive oil Sunflower oil V The present application is particularly con- 40 The F 1 b-Odymg or modification under equal conditions, decreases cerned ,with the modification of fatty oils'by means 0! polar compounds, i. e., modifying agents containing a positive charge in one part of the molecule and a negative charge in another part of the'moiecule, or capable of orienting their dirrerent radicals in opposite directions on an interbodied or modified by my methods,

in the order given. That is, the first mentioned oils are most extensively while the oils at the end of the series are modified to a lesser body. However, it should be also mentioned that by the employmentof suitable modifying agents in my methods;

pearing in the first 01 even the last mentioned oils of this series) can-be profoundbodied, as well as those oils apthe series.-

(those at the end ly modified or OH groups, for instance from ble,

ferred to may be treated per se. or they may be treated in mixtures containing more than one such oil, or containing other materials. For inor acids of fatty oils and of resins, may be modified in the invention.

separated fractions of fatty oils (for instance, the better drying fractions) may be used as starting materials, either alone or mixed with other oils.

The process of the present invention may. in fact, be used in connection with fatty oils themselves, fatty acids, esters of fatty acids, and variousanaterials containing the same. and it is to as limited to treatment 01' fatty oils Per se. since essentiall the same-reaction takes place in the case of treatment of the fatty acids, esters there- 'of, etc.

- Tn: Morn-mo Adm As hereinbefore mentioned, the present application isparticulariy concerned with the use of m agents having within the molecule an acidic inorganic nitrogenous residue. and an organic residue,

source. such as the treatment atmosphere or some materials present in the reaction. In any alsinquestionhaveineommonthecapabilityoi yielding a nitrogen-containing acid.

'fortherate sentsinthisciass Still further. agents in the class here involved eifect un extensive bodying of oils. in view of which the oil products are fast-drying. The products produced in accordance with the invention are. therefore, highly suitable for use in fastdrying water-resistant varnishes, for which there a is a considerable field of utility.

event, all of the materi- Agents falling in the above group may be or a number of different types, the following being representative:

Nltrobenzene Dinitro-chlorobenzene o-Nitrophenol Dini e p-Nitrophenol p-Nitro-acetanilide Dinitrobenzene 2:4-dinitrobenzene Nltro-chloro-benzene Nitro-aminobenzene Certain esters of inorganic acids have the important properties herein contemplated, for. instance- Nitrocresol carbonate Again, some salts of organic bases function in accordanc with the invention. For exam lem-Ni roaniline hydrochloride From the foregoing it win tain treating azents in the class herein claimed with (Serial Nos. 429,661and 429,663). I hate and claimed other 2-radical type t s? ing centshavingwithinthemoleculeahaloen residue or a sulphur-con in, but also the group claimed in said oonending application. ff

. fl'llum'l' CONDITION! ilcation is observable from even pending upon the extensive modification,

treatment or in a closed vessel;

. treatment conditions, matters are discussed pounds and varnish industry,-

minor amount (for instance, a

30%, ordinarily the amount required is relatively small, not usually more thanabout In general, the degree of modification of with increase in the amount of modifying agent used. The lower. limit depends somewhat on the particular agent and also on the particular oil being treated, although at least some modianywhere from a percentages, going down as low as .01%.

The treatment temperature may also be vari over a considerable range, depending upon the nature of the treating agent and of the oil, as well as on the character and extent sired. In general, the temperature should be considerably above room temperature, but not decomposition point of the on. a good working range is from about 100 the oil increases 5 of modification deproduct solid,

Sulphur may be used for this purpose and may be added as such, or in the form of a sulphur compound, such as sulphur chloride, etc. The action of the sulphur is analogous to that which takes place in'the vulcanization of rubber. Thus,

accelerators or activators (zinc oxide, etc.) or

, products, I employtemperatures between 120 to about 350 C., and preferablyabove about The time of treatment is also a variable. de-

treating agent, the starting material and the result desired. In general. in-,

creasing the time of treatment results in more and in most instances the at reaction temperature should be continued for at least minutes, and preferably Y for several hours.

The reaction may and either at sub-atmospheric, at atmospheric, or at super-atmospheric pressure. Different results are secured under ,various of. these conditions, as is brought out more fully in my copending application Serial 35,

With reference, to the foregoing statement of it is pointed out that these only briefly herein; since cation Serial No. 318,650, to which reference may be had for further information. This is also true as to the supplemental matters discussed just below.

take place eitherin an open 30 many of those products are useful as nishes,'lacquers and other liquid coating comand 180 C. for vulcanlzation, and'from 5 to 50 parts of sulphur to 100 parts of the isocolloid under treatment. This vulcanization should be eifected after modification, and accelerators and antioxidants may be added to the mix in 'known manner. I may produce liquid vulcanized products as well as rubber-like solids, by regulating "the amount of sulphur andthe time and temproducts are perature of heating. The liquid useful as varnish or paint bases. a

, Two step methods for making vulcanized, modified, heat-bodied fatty oil products are described and claimed in my application Serial No. 236,800v (Patent 2,234,545). .As there stated, rubber Others are useful for other purin the manufacture of varsubstitutes. poses, for instance,

positions, as well as in plastic compositions.

As noted above, the processes may be carried out in various ways, for instance, either in open or closed vessels as desired. In the latter case,

' the air can be enti'rel 'or artiall dis laced b they are fully disclosedinmy'copending appli- 40 y p y p y SUPPLEMENTAL Tsss'rmm'r Gonnmons sNn'Aann'rs My processes may be practiced in the absence of any additional material, other than the polar compound. However, I have found it is advantageous in some cases to compound in the presence of additional materials which facilitate .its incorporation and the modification of the organic isocolloid. For

instance, the polar compound may be incorpoincorporate the polar rated in the presence of various organic bodies such asthe purely organic additionsmentioned post anafter substantially above normal vulcanization temper-atures, the eifect the' sulphur treatment at modifying temperatures is quite diflerent from vulcanization.

However, I may modified products in also affect vulcanization of my an after treatment, so as to or partial absence of air, by

be advantageous alternate treatment increases the distribution of the polar compound in the another gas, such as hydrogen, CO2, S02, H28, nitrogen, etc., which influence the results obtained, these gases being used in supplement to the primary modifyin agent employed. Again, in both cases such gases may be passed through the material being treated. That is, the modification can be carried out during the passage of a gas. The gas pressure can be that of atmospheric. In many cases, however, a vacuum may be used with advantage. Again, evena higher pressure, of several atmospheres is to be recommended in That is, I have of the process vary with the nature of the gas present and also with the physical condition (pressure)' of this gas. Thus I have found that a certain given starting material which is initially liquid will sult of the modifying treatment, ifthe latter is become slightly viscous only as a reeifected under atmospheric pressure (open vesif the gas is rarefied by the used the ferent result from another gas or mixtures of gases such as mentioned ante. The modifying treatment may be carried out either in the total replacing the same with another gas, such as those shown ante.

be used, and I have found it to to use alternately,atmospheric or plus pressure and vacuum treatment. Such the uniformity oi treatment may coherent and elastic products, simi lar in some characteristics to ordinary rubbe used in my processes to vulcanized rubber-like certain cases, it being sometimes ad- I vantageous. I

further found that the results artial vacuum. In other cases treatment followed by a vacuum organic isocolloid. In my processes, the gas may 'bined with the treatment in my Serial No.

be blown or passed through the liquid simply both when open or closed vessels are employed to have a constant passage of the gas, such as those given ante, during the treatment with. polar compound. It may be stated with reference to the action of gases, that generally speaking rarefication of the gases present, by

processes.

If desired, the polar compound may be produced in situ, that is, within the organic isocolloid under treatment, by interaction within the organic isocolloid, of substances capable of reacting ,under the conditions of the process to reduce. the polar compound. The same applies to the gas in the isocolloid is to be treated and a substance or substances may be added which evolve the desired gas during the processing. It has been found in certain cases that polar compounds and gases which are produced in situ, being in the nascent state, are somewhat more active than those added in the pre-i'ormed state.

Likewise, the organic isocolloid itself may b formed in situ during the treatment. That is,

which has to be the production of such artificial or manufactured organic isocolloid may be advantageously comwith the polar commodified in a single step by heat- I bodying the fatty oil in the presence of themeand the cooperating action of gases in eflfecting the colloidal transformations characteristic of my invention,

ucts can be efi'ected by the addition to the material under treatment, of purely (i. e. metal-free) organic bodies, such as phenols, naphthols, naphthalene, chloroform, acetone, alcohols and their homol ues and 273,159 (Patent .other prior applications.

1,985,230) and- I have also found that inmy processe the the .use of rays of oscillating energy, such as ultra-violet rays, infra-red rays, X-rays, etc. That is, it is advantageous to irradiate the oil or other organic Example '1 300 partsoflinseed oilareheatedWithlS parts presence of which the organic produced before it can be treated,

-' an additional modification of the ultimate physical properties of the treated prodhours.

Example 2 ComAmrIvn Tnsrs Whereas profound changes in physical properties ofiatty oils usally require modifying agents in quantities of 1% or more, gradual changes of properties, such as bodying velocity, may be brought about with smaller proportions of modifying agent. Several comparative tests were carried out, using .5% 01' modifying instance the oil treated was alkali refined linseed oil.

In each test a batch of 300 grams of oil in a 1 liter aluminum beaker was heated at atmospheric pressure (the beaker being open) to 295 to 305 C. and kept at that temperature for 5 Two modifying agents were tried in this Visooel Reagent 1 of oil Blank 7 x Alpha-nitroso-beta- 16 Z-2 Nitroanthraquinon 12 2-6 Readings of both color and viscosity are en the Gardner scale.

Each of the above oils was further used in preparing a varnish, as follows 2 parts of oil product angnl part of ester gum were heated to 300 C. d kept at that temperature for 1 hour. The mixture was cooled to 200 C. and thinnedwith 3 parts of mineral spirits to 50%solids. Naphthenate driers were added in the proportion of .03% cobalt metal, .02% manganese metal and 3% lead metal, based on the quantity of oils used.

- The color and viscosity of the varnish in each case was asi'ollows;

Reagent Color of oViscosity1 Blank 11 A Alpha-nitroso-beta-napllthol 14 A Nitroanthraquinonm. 18+ A The foregoing varnishes were stored for 2 days and then panels of steel were coated with a coating knife yielding heavy films of .003" thickness.

Various characteristics of the varnishes were tested, with the following results.

. Over- Cold Boil- Alkali Reagent Inmal night water in reels. 3

' drying .33: reels. mag. alk5 'Blank' r vo- F ll t i l l vs V B F na 0 G NHl OSIWhISQIII- VG F 6 none G VG VG V0 V0 VG-ve 00d.

as s-bm'.

in preparing varnishes agent. In each cc. open of the panels expose for comparative purposes.

The cold water test was' made by immersing the panels iorzahoursincoldwarand ohservingthea earanceoitheiilm.

The boiling water test was madeby immersing the panels in boilins water tor is minutes, andcomparingtheresults. Inthiscasethedegreeoimilkinessandsoitnessotthenlmswas' observed as well as the speed with which the milky nlms returnedto their original appearance up n air drylnl. v

The'alkali resistancetestwas madebyimmersing the panels in a 3% sodium hydroxide solution and noting the time when the alkali completely attacked and dissolved the dime.

Examples 8-! In another series of comparative experiments, certain uniform treatment conditions were adopted, as follows:

In each case the oil employed was linseed oiland 5% of the treating agent was used.

In each case the heatlns time was inthe nei borhood hours. ments the appropriate reaction temperature was 300 0., although there were minor diilerences between various of the experiments. ment temperature was between about 290' to '.s1oc.-;- v

. A control experiment was also conducted under the same heating conditions, but without mung went. so as to secure comparative re- The experiments in this group may be divided into pairs, the 'twoexperiments of each pair employing the same treating agent. The diiterence between the treatment of the two members oieachpairwasasiollowsr I 1. Heating a 300 gram charge in a 1 liter disnask under vacuum-identified herebelow by the letter (a) following the example number. p

2. Heating a 150 or 300 gram charge'in a 500 enameled low by the letter (is) iollowing the example number. a Examples) v o flitrophcnol The reagent dissolved at about 81' C.

Dur-

,ingriseintemperature somebumplng andslight.

volatilizatlon took place. At treatment temperature the mixture boiled steadily, and after about 2 hours began to thicken, reaching an almost solid condition. Additional heating caused some.

thinning. The product was 'a black sticky mass, which was somewhat plastic. r

Example 3 (b) o-Nitropnenol Some boiling occurred durin rise in temperature and the mixture then subsided. In addition a small amount 01 reagent sublimed at about 240 0. Boiling took place throughout most oi the time on temperature.

The product was a highly visc us sticky liquid, dark brown in color, with a green appearance in reflected light.

w some explosions as temperature was reached beaker-identified herebe- 75' consistency of aaespie 5' Example uh treatment temperature and the mixture began to thicken in about 8% hmt which time Toward the end at the treatment time the mixture again commenced to thin so that the prod: act was poured out alter about 4 hours and minutes.

m The product was a semi-solid dark brown elastic' mass.

The distillate settled in two layers the bottom layer being clear and the top layer a red I Example lib) Dinimmiline oil.

which time the tumes'had subsided. After about 2 and Y hours on temperature the mixture had iellied. Contlnuedheating showed no signs of thinning and the mixture was then poured out,

so an explosion occurring when ouring the last por- In conducting these experltions.

The product was a black rubbery jelly.

' Example 5(a) as j p-Nitrophenol The mixture very promptly irothed. but alter reaching about 180 to 190 C. the trothing subsided and a very vigorous reaction took place,

0 lasting some two or three minutes. The mixture commenced to boil steadily at about 293' C.- and this was continued tor 2% hours. Continued heating caused The product was a semi-solid dark brown elastic mass.

' The'distillate subsided and formed two layers,

the bottom layer being about 1 cc. of a faint yellow liquid and thetop layer about 20 cc. of dark oil. p g

' lixampl flbl 'r-Nitrophenol' On initial heating irothing'oeeurred but this promptly-subsided and at about 296' 0. yellow 'iumes we're evolved. The product was a very thick sticky dark brown oil with a dull. green fluorescence.

p-Nitro ocetonilide Badirothing occurredduringinitlalrisein temperature and distillation oi reagent also set in. The temperature was kept below about 200 Aldo: 1% hours to prevent loss of reagent. Gentie boiling ccurred on temperature.

'I'heproductwasablackstic semi-solidmasl.

amn sia p-Nitro aoetanilidc sum mam: on initialheating, but this rapidly subsided.- The mixture darkened and thickened while on temperature.

The product was brown in color and of the Example 7(a) p-Nitro chlorobenzene Boiling set in at about 250 C. and some bumping followed shortly. However, on temperature the mixture soon subsided.

The product was a fairly viscous oil of dark brown color.

Example 70)) p-Nitro chlorobenzene Thebest dryingwasthevarnishmadewith the product of Example 4(a) in sequence as indicated.

I claim: e 1. In the modification of fatty oils to improve their drying properties, the process which comprises mixing the oil with a minor amount'and not more than 10% of a polar compound having within the molecule an organic residue, and an acidic inorganic nitrogenous residue capable of yielding a nitrogen-containing acid, and heating the mixture to a reaction temperature between about-200 and 350 utes.

2. In the modification of fatty oils to improve their drying properties, the process which comprises mixing the oil with a minor amount and not more than 10% of an organic nitrocompound, and heating the mixture to a reaction temperature between about 200 and 350 C. for at least thirty minutes.

3. A process in accordance with claim 2 in 13-0 n beaker experiment. Visco i ty-range from heavy to light.

Color-range from dark to light.

varnishes were made up employing the prodtive.

ucts of Experiments 3 to 'l, the varnishes being without driers. The relative drying order of the varnishes is indicated in the following list:

1 D v ExampeNo a a (g; 9 a l b; 2 a 11 a) 1 9 0 (b? a Blank 7 which the fatty Example Viscosity Color Reagent solubility 3(a)-V .p-Nitroaeetanilide Medium soit (solid).-- Fairly dark p-Nitroacetanilidem Med. viscous (liquid)- Light (medium).--.'

o-Nitrophenol. Soft solid rumour Dr in a min. at

o-Nitrophenoi do do Dissolves in 5-10 min.

5(a) v below 0.

Dinitraniline an do sac-n blnjmnm e sin [in so -v p-Niirophenol..-. -l Thick visoous(fluid).. Partundissolved.

sun-n mt hmi Boit solid Fairly dark Do.

p-Nitrochlorbenzene Med. viscous (liquid); Medium (greenish-brown)" Diseolves. 7(b)-B a p-Nitrochlorbenzene. A ---do.- Light(mod.greenish) Do.

Blank -Q m. was (liquid)- Light Code explanation:

V-vacuum experiment.

which said nitrocompound is abenzol deriva- 4. A process in which the nitroderivative.

5. A process compound is a naphthalene in accordanc e with claim 2 in oil is linseed oil.

LAszLo AUER..-

the othersiollowing C. for at least thirty min-- accordance with claim 2 in 

